JP2826341B2 - Method for manufacturing solid electrolytic capacitor - Google Patents
Method for manufacturing solid electrolytic capacitorInfo
- Publication number
- JP2826341B2 JP2826341B2 JP1119791A JP11979189A JP2826341B2 JP 2826341 B2 JP2826341 B2 JP 2826341B2 JP 1119791 A JP1119791 A JP 1119791A JP 11979189 A JP11979189 A JP 11979189A JP 2826341 B2 JP2826341 B2 JP 2826341B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- polymerization
- pyrrole
- electrolytic polymerization
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003990 capacitor Substances 0.000 title claims description 27
- 239000007787 solid Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 65
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 24
- 229920000128 polypyrrole Polymers 0.000 claims description 21
- 239000011888 foil Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007784 solid electrolyte Substances 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000007796 conventional method Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 28
- 239000008151 electrolyte solution Substances 0.000 description 7
- 229920006254 polymer film Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012212 insulator Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、導電性高分子であるポリピロールを固体電
解質として使用する固体電解コンデンサの製造方法に関
し、更に詳しくは、化成箔上へのピロールの電解重合工
程を改良して、電解重合の容易化および確実化を図る固
体電解コンデンサの製造方法に関する。The present invention relates to a method for producing a solid electrolytic capacitor using a conductive polymer, polypyrrole, as a solid electrolyte. More specifically, the present invention relates to a method for producing pyrrole on a chemical conversion foil. The present invention relates to a method for manufacturing a solid electrolytic capacitor which improves an electrolytic polymerization step to facilitate and ensure electrolytic polymerization.
［従来の技術］ 電解コンデンサは、小形、大容量、安価で整流出力の
平滑化等に優れた特性を示し、各種電気・電子機器の重
要な構成要素の１つである。一般に電解コンデンサには
電解液式と固体式とがあり、前者が、陽極と陰極との間
に電解液を介在させるのに対し、後者は、二酸化マンガ
ン、二酸化鉛、テトラシアノキノジメタン錯塩またはポ
リピロールのような導電性の酸化物または有機物を固体
電解質として介在させる。電解液式の電解コンデンサ
は、液状の電解質を使用するイオン伝導によるため、高
周波領域において著しく抵抗が増大しインピーダンスが
増大する。したがって、高周波特性の点では、固体電解
コンデンサの方が格段に優れている。2. Description of the Related Art Electrolytic capacitors are small, large-capacity, inexpensive, and have excellent characteristics such as smoothing of rectified output, and are one of important components of various electric and electronic devices. In general, electrolytic capacitors include an electrolytic solution type and a solid type, and the former has an electrolytic solution interposed between the anode and the cathode, whereas the latter has manganese dioxide, lead dioxide, tetracyanoquinodimethane complex salt or A conductive oxide or organic substance such as polypyrrole is interposed as a solid electrolyte. Since the electrolytic solution type electrolytic capacitor is based on ionic conduction using a liquid electrolyte, the resistance significantly increases and the impedance increases in a high frequency region. Therefore, in terms of high-frequency characteristics, solid electrolytic capacitors are much better.
固体電解コンデンサに用いる固体電解質としては、固
体電解質自体の導電性や安定性、並びに用いる固体電解
質の性質によって規定される電解コンデンサの静電容量
（Cap）、誘電正接（tanδ）、漏れ電流（LC）、等価直
列抵抗（ESR）等の指標から、ポリピロールが最も優れ
ていると考えられる。As the solid electrolyte used for the solid electrolytic capacitor, the conductivity and stability of the solid electrolyte itself, and the capacitance (Cap), dielectric loss tangent (tanδ), leakage current (LC ) And the equivalent series resistance (ESR), polypyrrole is considered to be the best.
ポリピロールを固体電解質として用いる固体電解コン
デンサは、例えば、特開昭63−173313号に記載されてい
る。一般に、この種の固体電解コンデンサを製造する際
は、化学的重合および電解重合により陽極箔上にポリピ
ロールの薄膜を形成し、その後この表面に銀ペーストの
ような導電ペーストを用いて端子を接着して対極リード
を取出し、エポキシ樹脂等で外装してコンデンサ製品を
作製する。A solid electrolytic capacitor using polypyrrole as a solid electrolyte is described, for example, in JP-A-63-173313. Generally, when manufacturing this type of solid electrolytic capacitor, a polypyrrole thin film is formed on the anode foil by chemical polymerization and electrolytic polymerization, and then the terminals are bonded to this surface using a conductive paste such as silver paste. Take out the counter electrode lead and cover it with epoxy resin or the like to make a capacitor product.
誘電体酸化被膜上にピロールの電解重合膜を形成させ
るに際しては、習慣的に直流電流が使用されている。こ
れは、ポリピロールの電解コンデンサの固体電解質とし
ての使用が開発される以前に、電解コンデンサの固体電
解質としての使用以外を目的として一般的にピロールの
電解重合を行う場合に直流電流が常用されていたことが
踏襲されたものと考えられる。In forming an electropolymerized film of pyrrole on a dielectric oxide film, a direct current is customarily used. This was because, before the use of polypyrrole as a solid electrolyte for electrolytic capacitors was developed, DC current was commonly used when performing electrolytic polymerization of pyrrole generally for purposes other than the use as a solid electrolyte for electrolytic capacitors. It is thought that this was followed.
ピロールの電解重合は、直流および交流のいずれによ
っても行うことができるが、誘電体酸化被膜上にポリピ
ロールの電解重合膜を形成させる際には、誘電体酸化被
膜の物理化学的特徴を十分に考慮する必要があることが
これまで看過されていた。従来は習慣的に直流による電
解重合を行っていたために、誘電体酸化被膜上に直接電
解重合膜を形成させることは困難であった。アルミニウ
ム酸化被膜である誘電体被膜は実質的に絶縁体であり、
このような絶縁膜に対しては、直流電流の流れを期待す
る直流による電解重合は必ずしも合理的なものとはいえ
ない。The electropolymerization of pyrrole can be performed by either direct current or alternating current.However, when forming the polypyrrole electropolymerized film on the dielectric oxide film, the physicochemical characteristics of the dielectric oxide film must be sufficiently considered. What you need to do has been overlooked. Conventionally, it has been difficult to form an electropolymerized film directly on a dielectric oxide film because electropolymerization by direct current has been customarily performed. The dielectric coating, which is an aluminum oxide coating, is substantially an insulator,
For such an insulating film, it is not always reasonable to perform electrolytic polymerization by DC, which is expected to flow DC current.
直流による電解重合のみでは誘電体酸化被膜上におけ
るポリピロール膜形成が必ずしも十分ではないため、従
来は電解重合を行う前に化学重合を行うことによりポリ
ピロールを予備重合させる工程が不可欠であった。ポリ
ピロール重合膜形成に真に必要な工程は電解重合工程で
あるため、化学的重合工程のような予備的工程を省略ま
たは簡略化することができれば、製造効率の向上を図り
得ると考えられる。Since the formation of a polypyrrole film on a dielectric oxide film is not always sufficient only by electrolytic polymerization using a direct current, conventionally, a step of prepolymerizing polypyrrole by performing chemical polymerization before performing electrolytic polymerization has been indispensable. Since a process truly required for forming a polypyrrole polymer film is an electrolytic polymerization process, it is considered that if a preliminary process such as a chemical polymerization process can be omitted or simplified, manufacturing efficiency can be improved.
［発明が解決しようとする課題］ 本発明は、導電性高分子であるポリピロールを固体電
解質として使用する固体電解コンデンサを製造するに際
し、化成箔上へのピロールの電解重合工程を改良して、
絶縁体たる誘電体酸化被膜の物理化学的特徴により合致
した方法で電解重合によるポリピロール重合膜の形成を
行い、ピロール重合工程の容易化、簡略化および確実化
を図り、これにより安定した品質の重合膜形成を期する
と共に製造工程全体の効率向上を図る固体電解コンデン
サの製造方法を提供することを目的とする。[Problems to be Solved by the Invention] The present invention, when producing a solid electrolytic capacitor using polypyrrole, which is a conductive polymer, as a solid electrolyte, by improving the electrolytic polymerization step of pyrrole on a chemical conversion foil,
Forming a polypyrrole polymer film by electrolytic polymerization in a method that more closely matches the physicochemical characteristics of the dielectric oxide film, which is the insulator, to facilitate, simplify, and assure the pyrrole polymerization process, and thereby achieve stable quality polymerization. It is an object of the present invention to provide a method for manufacturing a solid electrolytic capacitor that ensures film formation and improves the efficiency of the entire manufacturing process.
［課題を解決するための手段］ 本発明によれば、電解酸化による表面酸化被膜を有す
る化成箔上へのピロールの電解重合を行うことにより形
成されるポリピロール膜を固体電解質とする固体電解コ
ンデンサを製造するに際し、電解液中にて交流電解条件
下でピロールの電解重合を行うことにより、酸化被膜上
に直接電解重合膜を形成させることを特徴とする固体電
解コンデンサの製造方法が提供される。[Means for Solving the Problems] According to the present invention, there is provided a solid electrolytic capacitor using a polypyrrole film formed by performing electrolytic polymerization of pyrrole on a conversion foil having a surface oxide film by electrolytic oxidation as a solid electrolyte. In the production, a method for producing a solid electrolytic capacitor is provided, wherein an electrolytic polymerization film is formed directly on an oxide film by performing electrolytic polymerization of pyrrole in an electrolytic solution under AC electrolytic conditions.
波形をパルス重畳または高周波重畳の正弦波または歪
波とし、正弦波または歪波の周波数を1Hz〜100kHz、好
ましくは10Hz〜100kHzとし、電流密度を1mA/cm2〜1A/cm
2とする交流電解条件下でピロールの電解重合を行えば
好適である。The waveform is a sine wave or distorted wave of pulse superposition or high frequency superposition, the frequency of the sine wave or distorted wave is 1 Hz to 100 kHz, preferably 10 Hz to 100 kHz, and the current density is 1 mA / cm 2 to 1 A / cm
It is preferable to perform the electrolytic polymerization of pyrrole under the AC electrolysis conditions of 2 .
気相重合のような常法によりピロールの化学重合を行
った後に、ピロールの電解重合を交流によって行うこと
もできる。After performing chemical polymerization of pyrrole by a conventional method such as gas phase polymerization, electrolytic polymerization of pyrrole can be performed by alternating current.
電解酸化による表面酸化被膜を有する化成箔は、通常
は表面を電解酸化によって酸化被膜誘電体に変えて化成
したアルミニウムフィルムとする。A conversion foil having a surface oxide film formed by electrolytic oxidation is usually an aluminum film whose surface is converted to an oxide film dielectric by electrolytic oxidation.
ピロールモノマを0.01〜3.0M/lの濃度で電解重合用溶
媒に溶解すれば好適である。It is preferable to dissolve the pyrrole monomer in a solvent for electrolytic polymerization at a concentration of 0.01 to 3.0 M / l.
電解重合用支持電解質を0.01〜2M/lのBST/AN溶液（た
だし、BST:ボロジサリチル酸トリエチルアミン塩または
トリエチルアンモニウムボロジサリチレート、AN:アセ
トニトリル）とすれば好適である。その他、プロピレン
カーボネート、γ−ブチロラクトン、1,2−ジメトキシ
エタン等を電解重合用溶媒として使用することができ
る。なお、交流電解の電解液は、基本的には直流の電解
液と同様のものを使用し得る。It is preferable that the supporting electrolyte for electrolytic polymerization is a 0.01 to 2 M / l BST / AN solution (BST: triethylamine borodisalicylate or triethylammonium borodisalicylate, AN: acetonitrile). In addition, propylene carbonate, γ-butyrolactone, 1,2-dimethoxyethane, and the like can be used as a solvent for electrolytic polymerization. Note that, as the electrolytic solution for AC electrolysis, basically the same one as the direct current electrolytic solution can be used.
交流による電解重合は、好ましくは常温により行う。 The electrolytic polymerization by alternating current is preferably performed at room temperature.
気相重合は、例えば、10％の(NH4)2S2O8水溶液に含浸
した後、常温（10〜30℃）常圧下でピロール蒸気中に10
分間放置することにより行う。In the gas phase polymerization, for example, after impregnating with 10% (NH 4 ) 2 S 2 O 8 aqueous solution, 10%
Perform by letting stand for minutes.
前記した方法によって化成箔上にポリピロール重合膜
を形成させた後、常法により素子化し、封止して製品化
する。After a polypyrrole polymer film is formed on the chemical conversion foil by the above-described method, the device is formed into an element by a conventional method, sealed, and commercialized.
［作用］ アルミニウム酸化被膜である誘電体被膜は実質的に絶
縁体であり、このような絶縁膜に対しては、直流による
電解重合は必ずしも合理的なものではない。絶縁膜上へ
重合膜を形成させる場合、交流の方が容易に電流を流す
ことができる。本発明による方法は、実質的に絶縁体で
ある誘電体被膜の物理化学的性質により合致するもので
ある。[Operation] The dielectric film, which is an aluminum oxide film, is substantially an insulator, and direct current electrolytic polymerization is not necessarily rational for such an insulating film. When a polymer film is formed on an insulating film, an alternating current allows a current to flow more easily. The method according to the invention is more compatible with the physicochemical properties of a dielectric film which is substantially an insulator.
直流による電解重合のみでは誘電体酸化被膜上におけ
るポリピロール膜形成が必ずしも十分ではないため、従
来は電解重合を行う前に化学重合を行うことによりポリ
ピロールを予備重合させる工程が不可欠であった。本発
明によれば、ポリピロール重合膜形成に真に必要な電解
重合工程がより充実したものとなるため、化学的重合工
程のような予備的工程を省略または簡略化することがで
き、製造効率の向上を図ることができる。Since the formation of a polypyrrole film on a dielectric oxide film is not always sufficient only by electrolytic polymerization using a direct current, conventionally, a step of prepolymerizing polypyrrole by performing chemical polymerization before performing electrolytic polymerization has been indispensable. According to the present invention, since the electrolytic polymerization step truly required for forming the polypyrrole polymer film becomes more substantial, a preliminary step such as a chemical polymerization step can be omitted or simplified, and the production efficiency can be reduced. Improvement can be achieved.
直流による電解重合を行う場合は、電流が一方向にし
か流れないため、１回の電解重合で１枚の化成箔しか処
理できない。すなわち、一方の極を化成箔とし、他方の
極は化成箔以外の適当な対極とする必要がある。これに
対し、交流による電解重合を行う場合は、対極を必要と
せず、両方の極を化成箔とすることができ、１回の電解
重合で２枚の化成箔を処理することができるため、製造
効率が向上する。In the case of performing electrolytic polymerization by direct current, current flows in only one direction, so that only one chemical conversion foil can be processed in one electrolytic polymerization. That is, it is necessary to use one electrode as a chemical conversion foil and the other electrode as an appropriate counter electrode other than the chemical conversion foil. On the other hand, when performing the electrolytic polymerization by alternating current, the counter electrode is not required, and both electrodes can be formed into chemical conversion foils, and two chemical conversion foils can be processed by one electrolytic polymerization. Manufacturing efficiency is improved.
［発明の効果］ 本発明によれば、導電性高分子であるポリピロールを
固体電解質として使用する固体電解コンデンサを製造す
るに際し、化成箔上へのピロールの電解重合工程を改良
して、絶縁体たる誘電体酸化被膜の物理化学的特徴によ
り合致した方法で電解重合によるポリピロール重合膜の
形成を行い、ピロール重合工程の容易化、簡略化および
確実化を図り、これにより安定した品質の重合膜形成を
期すると共に製造工程全体の効率向上を図る固体電解コ
ンデンサの製造方法が提供される。[Effects of the Invention] According to the present invention, when manufacturing a solid electrolytic capacitor using polypyrrole, which is a conductive polymer, as a solid electrolyte, the process of electrolytic polymerization of pyrrole on a chemical conversion foil is improved to be an insulator. A polypyrrole polymer film is formed by electrolytic polymerization in a method that matches the physicochemical characteristics of the dielectric oxide film, and the pyrrole polymerization process is simplified, simplified, and assured, thereby forming a stable quality polymer film. The present invention provides a method for manufacturing a solid electrolytic capacitor which improves the efficiency of the entire manufacturing process.
［実施例］ 以下に実施例により本発明を更に詳細に説明するが、
本発明は以下の実施例にのみ限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited only to the following examples.
実施例１ 第１図に示すように、50Vで化成した2.2mm巾×10mmの
大きさのリード付きアルミニウム化成箔10を用い、0.1M
/lのピロールモノマを0.1M/lのBST/AN溶液中に溶解した
電解液からなる浴12中にて、交流電源14を使用し、常温
で交流による電解重合を行った。交流電解条件は、10mA
/cm2、20Hz、60分とした。その後、導電ペーストで陰極
を取出し、樹脂で外装して製品化し、固体電解コンデン
サを製造した。Example 1 As shown in FIG. 1, a lead-formed aluminum chemical conversion foil 10 having a size of 2.2 mm width × 10 mm formed at 50 V was used.
In a bath 12 consisting of an electrolytic solution obtained by dissolving / l pyrrole monomer in a 0.1 M / l BST / AN solution, an AC power supply 14 was used to perform electrolytic polymerization at room temperature using an AC power supply 14. AC electrolysis condition is 10mA
/ cm 2 , 20 Hz, and 60 minutes. Thereafter, the cathode was taken out with a conductive paste, and was packaged with a resin to produce a product, and a solid electrolytic capacitor was manufactured.
実施例２ 電解重合を行う前に、10％(NH4)S2O4水溶液に含浸
後、常温・常圧下でピロール蒸気雰囲気に10分間放置す
ることにより気相化学重合を行った以外は実施例１と同
様にして固体電解コンデンサを製造した。Example 2 Before performing the electrolytic polymerization, a 10% (NH 4 ) S 2 O 4 aqueous solution was impregnated, and then a gas phase chemical polymerization was performed by leaving the mixture in a pyrrole vapor atmosphere at normal temperature and normal pressure for 10 minutes. A solid electrolytic capacitor was manufactured in the same manner as in Example 1.
比較例１ 交流による電解重合を行う代りに直流による電解重合
を行い、直流電解条件として0.1M/lBST−AN溶液、0.1M/
lピロール、5mA/cm2、60分とする以外は実施例１と同様
にして固体電解コンデンサを製造した。Comparative Example 1 Instead of performing the electrolytic polymerization using an alternating current, electrolytic polymerization using a direct current was performed instead of performing the electrolytic polymerization using an alternating current, and the 0.1 M / l BST-AN solution, 0.1 M /
A solid electrolytic capacitor was manufactured in the same manner as in Example 1 except that l-pyrrole, 5 mA / cm 2 , and 60 minutes were used.
比較例２ 交流による電解重合を行う代りに直流による電解重合
を行い、直流電解条件として比較例１と同様とする以外
は実施例２と同様にして固体電解コンデンサを製造し
た。Comparative Example 2 A solid electrolytic capacitor was manufactured in the same manner as in Example 2 except that the electrolytic polymerization was performed using a direct current instead of the electrolytic polymerization using an alternating current.
以上のようにして製造したポリピロール固体電解コン
デンサの製品特性の測定結果を次の表に示す。The following table shows the measurement results of the product characteristics of the polypyrrole solid electrolytic capacitor manufactured as described above.
製品特性に関して検討すると、交流による電解重合の
みを行う実施例１と、直流による電解重合に化学重合を
加えた比較例２とを比較した場合、本発明による方法で
は直接酸化被膜上へ電解重合を行うため、特に含浸率の
点では不利であるが、他の特性については同程度であ
り、製品としては十分な固体電解コンデンサを得ること
ができ、製造工程の簡略化という目的は少くとも達成さ
れている。製品特性の観点から見た場合には、交流電解
重合のみの実施例１は、直流電解重合のみの比較例１よ
り優れるが、直流電解重合に化学重合を加えた比較例２
にはやや劣るといえる。交流電解による電解重合に化学
重合を加えた実施例２は、直流による電解重合に化学重
合を加えた比較例２より良好であり、実際の製造に際し
ては、要求される製品特性と製造コストとを勘案して、
適切な製造方法を選択すべきである。 When examining the product characteristics, when comparing Example 1 in which only electrolytic polymerization by AC is performed and Comparative Example 2 in which chemical polymerization is added to electrolytic polymerization in direct current, the method according to the present invention directly performs the electrolytic polymerization on the oxide film. Therefore, it is disadvantageous particularly in terms of the impregnation rate, but other characteristics are almost the same, a sufficient solid electrolytic capacitor can be obtained as a product, and the object of simplifying the manufacturing process is at least achieved. ing. From the viewpoint of product characteristics, Example 1 using only AC electrolytic polymerization is superior to Comparative Example 1 using only DC electrolytic polymerization, but Comparative Example 2 using DC electrolytic polymerization and chemical polymerization added thereto.
Is somewhat inferior. Example 2 in which chemical polymerization was added to electrolytic polymerization by AC electrolysis was better than Comparative Example 2 in which chemical polymerization was added to electrolytic polymerization by direct current. In actual production, required product characteristics and production costs were reduced. Considering
Appropriate manufacturing methods should be selected.
第１図は交流電解重合の概略を示す図である。 10…化成箔、12…浴 14…交流電源 FIG. 1 is a diagram schematically showing AC electrolytic polymerization. 10 ... chemical foil, 12 ... bath 14 ... AC power supply
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安藤 進 東京都青梅市東青梅１丁目167番地の１ 日本ケミコン株式会社内 (56)参考文献 特開 昭63−173313（ＪＰ，Ａ) 特開 昭63−48750（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01G 9/028──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Susumu Ando 1-17-1 Higashi-Ome, Ome-shi, Tokyo Nippon Chemi-Con Corporation (56) References JP-A-63-173313 (JP, A) JP-A-63 -48750 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) H01G 9/028
Claims (3)
箔上へのピロールの電解重合を行うことにより形成され
るポリピロール膜を固体電解質とする固体電解コンデン
サを製造するに際し、電解液中にて波形をパルス重畳ま
たは高周波重畳の正弦波または歪波とする交流電解条件
下でピロールの電解重合を行うことにより、酸化被膜上
に直接電解重合膜を形成させることを特徴とする固体電
解コンデンサの製造方法。1. A method for producing a solid electrolytic capacitor using a polypyrrole film formed by performing electrolytic polymerization of pyrrole on a conversion foil having a surface oxide film by electrolytic oxidation as a solid electrolyte. A method for producing a solid electrolytic capacitor, wherein an electrolytic polymerization film is formed directly on an oxide film by performing electrolytic polymerization of pyrrole under AC electrolytic conditions in which a sine wave or a distortion wave of pulse superposition or high frequency superposition is used. .
z、好ましくは10Hz〜100kHzとし、電流密度を1mA/cm2〜
1A/cm2とする交流電解条件下でピロールの電解重合を行
う請求項１記載の方法。2. The frequency of a sine wave or a distorted wave is 1 Hz to 100 kHz.
z, preferably 10 Hz to 100 kHz, and the current density is 1 mA / cm 2 to
The method of claim 1, wherein performing the electrolytic polymerization of pyrrole in the alternating current electrolysis conditions to 1A / cm 2.
に、ピロールの電解重合を交流によって行う請求項１記
載の方法。3. The method according to claim 1, wherein after the chemical polymerization of pyrrole is performed by a conventional method, the electrolytic polymerization of pyrrole is performed by alternating current.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1119791A JP2826341B2 (en) | 1989-05-13 | 1989-05-13 | Method for manufacturing solid electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1119791A JP2826341B2 (en) | 1989-05-13 | 1989-05-13 | Method for manufacturing solid electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02299213A JPH02299213A (en) | 1990-12-11 |
| JP2826341B2 true JP2826341B2 (en) | 1998-11-18 |
Family
ID=14770314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1119791A Expired - Fee Related JP2826341B2 (en) | 1989-05-13 | 1989-05-13 | Method for manufacturing solid electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2826341B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8026137B2 (en) | 2003-10-20 | 2011-09-27 | Showa Denko K.K. | Production method of a capacitor |
| US8349683B2 (en) | 2003-09-26 | 2013-01-08 | Showa Denko K.K. | Production method of a capacitor |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2714077B1 (en) * | 1993-12-21 | 1996-03-08 | Lorraine Laminage | Process and bath for the electroplating of polypyrrole on a surface of metal which can be oxidized by electropolymerization. |
| US7842103B2 (en) | 2005-06-30 | 2010-11-30 | Showa Denko K.K. | Method for manufacturing solid electrolytic capacitor device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0679488B2 (en) * | 1986-08-18 | 1994-10-05 | 三洋電機株式会社 | Secondary battery |
| JPS63173313A (en) * | 1987-01-13 | 1988-07-16 | 日本カーリット株式会社 | solid electrolytic capacitor |
-
1989
- 1989-05-13 JP JP1119791A patent/JP2826341B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8349683B2 (en) | 2003-09-26 | 2013-01-08 | Showa Denko K.K. | Production method of a capacitor |
| US8026137B2 (en) | 2003-10-20 | 2011-09-27 | Showa Denko K.K. | Production method of a capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02299213A (en) | 1990-12-11 |
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